Bromine containing silicon precursors for encapsulation layers

ABSTRACT

Methods of depositing silicon nitride encapsulation layers by atomic layer deposition over memory devices including chalcogenide material are provided herein. Methods include using iodine-containing and/or bromine-containing silicon precursors and depositing thermally using ammonia or hydrazine as a second reactant, or iodine-containing and/or bromine-containing silicon precursors and depositing using a nitrogen-based or hydrogen-based plasma.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No. 15/272,222, filed on Sep. 21, 2016 and titled “BROMINE CONTAINING SILICON PRECURSORS FOR ENCAPSULATION LAYERS,” which is a continuation-in-part of U.S. patent application Ser. No. 14/935,317 filed on Nov. 6, 2015, issued on Mar. 21, 2017 at U.S. Pat. No. 9,601,693, and titled “METHOD FOR ENCAPSULATING A CHALCOGENIDE MATERIAL,” which claims benefit of U.S. Provisional Patent Application No. 62/232,243, filed Sep. 24, 2015, and titled “METHOD FOR ENCAPSULATING A CHALCOGENIDE MATERIAL WITH MINIMAL DAMAGE TO CHALCOGENIDE MATERIAL AND WITHOUT METAL CONTAMINATION WHILE MINIMIZING THERMAL CROSS TALK,” which are all incorporated by reference herein in their entireties and for all purposes.

BACKGROUND

Semiconductor device fabrication may involve deposition of silicon nitride films. Silicon nitride thin films have unique physical, chemical, and mechanical properties and thus are used in a variety of applications. For example, silicon nitride films may be used in diffusion barriers, gate insulators, sidewall spacers, encapsulation layers, strained films in transistors, and the like. Conventional methods of depositing silicon nitride films may damage components of the process chamber where deposition is performed, or may damage substrate materials.

SUMMARY

Provided herein are methods of processing substrates.

One aspect involves a method of encapsulating chalcogenide material, the method including: (a) providing a substrate to a chamber, the substrate including one or more exposed layers of the chalcogenide material; (b) exposing the substrate to a chlorine-free bromine-containing silicon precursor under conditions allowing the chlorine-free bromine-containing silicon precursor to adsorb onto the surface of the substrate, thereby forming an adsorbed layer of the chlorine-free bromine-containing silicon precursor; and (c) exposing the substrate to a second reactant to form a silicon nitride film on the chalcogenide material.

In various embodiments, the chlorine-free bromine-containing silicon precursor is any of compounds having a chemical formula of Si_(x)Br_(y)I_(z), where x=1, y is an integer between and including 1 and 4, and y+z=4; and compounds having a chemical formula of Si_(x)Br_(y)I_(z), where x=2, y is an integer between and including 1 and 6, and y+z=6.

For example, in some embodiments, the chlorine-free bromine-containing silicon precursor is any of tetrabromosilane (SiBr₄), SiBr₃I, SiBr₂I₂, SiBrI₃, hexabromodisilane (Si₂Br₆), Si₂Br₅I, Si₂Br₄I₂, Si₂Br₃I₃, Si₂Br₂I₄, Si₂BrI₅, and combinations thereof.

In various embodiments, the silicon nitride is deposited to a thickness of at least about 40 Å. In various embodiments, the second reactant is any of ammonia and hydrazines, and the silicon nitride may be deposited at a temperature less than about 300° C. For example, in some embodiments, silicon nitride is deposited at a temperature between about 50° C. and about 300° C. In some embodiments, silicon nitride is deposited at a temperature between about 200° C. and about 275° C.

In some embodiments, the method also includes igniting a plasma when exposing the substrate to the second reactant to generate a reactive species. In some embodiments, the second reactant is either nitrogen or hydrogen.

In various embodiments, the second reactant forms a volatile species when reacted with any of aluminum, iron, copper, antimony, selenium, tellurium, germanium, and arsenic. In some embodiments, the chalcogenide material is any of sulfur, selenium, tellurium, and combinations thereof.

In some embodiments, the silicon nitride film deposited has a step coverage of at least about 95%. The silicon nitride film may be deposited to a thickness greater than about 30 Å.

In various embodiments, the chamber is purged during at least one of: (i) after performing (b) and prior to performing (c); and (ii) after performing (c). In some embodiments, (b) and (c) are repeated sequentially. In various embodiments, the chamber is purged by flowing a purge gas such as any of argon, helium, nitrogen, and hydrogen.

One aspect involves a method of encapsulating chalcogenide material by (a) providing a substrate to a chamber, the substrate including one or more exposed layers of the chalcogenide material; (b) exposing the substrate to a chlorine-free iodine-containing silicon precursor under conditions allowing the chlorine-free iodine-containing silicon precursor to adsorb onto the surface of the substrate, thereby forming an adsorbed layer of the chlorine-free iodine-containing silicon precursor; and (c) exposing the substrate to a second reactant to form a silicon nitride film on the chalcogenide material.

The chlorine-free iodine-containing silicon precursor may be any of diiodosilane, tetraiodosilane, and hexaiodosilane. In various embodiments, the second reactant is any of ammonia and hydrazines, and the silicon nitride may be deposited at a temperature less than about 300° C. For example, in some embodiments, silicon nitride is deposited at a temperature between about 50° C. and about 300° C. In some embodiments, silicon nitride is deposited at a temperature between about 200° C. and about 275° C.

In some embodiments, the method also includes igniting a plasma when exposing the substrate to the second reactant to generate a reactive species. In some embodiments, the second reactant is either nitrogen or hydrogen.

In various embodiments, the second reactant forms a volatile species when reacted with any of aluminum, iron, copper, antimony, selenium, tellurium, germanium, and arsenic. In some embodiments, the chalcogenide material is any of sulfur, selenium, tellurium, and combinations thereof.

In some embodiments, the silicon nitride film deposited has a step coverage of at least about 95%. The silicon nitride film may be deposited to a thickness greater than about 30 Å.

In various embodiments, the chamber is purged during at least one of: (i) after performing (b) and prior to performing (c); and (ii) after performing (c). In some embodiments, (b) and (c) are repeated sequentially. In various embodiments, the chamber is purged by flowing a purge gas such as any of argon, helium, nitrogen, and hydrogen.

In some embodiments, the method further includes depositing a second layer over the substrate, whereby the layer is deposited with a step coverage of between about 30% and about 90%.

The second layer may be deposited by remote plasma chemical vapor deposition or plasma enhanced chemical vapor deposition. In various embodiments, the second layer may include silicon nitride. In some embodiments the second layer may include silicon carbide.

In various embodiments, the substrate includes one or more features, and the second layer is deposited non-conformally such that thickness of the second layer on a sidewall of at least one of the one or more features is greater at the top of the at least one of the one or more features than thickness of the second layer on the sidewall of the at least one of the one or more features at the bottom of the at least one of the one or more features.

Another aspect involves a memory device including: a memory stack including a chalcogenide material; a silicon nitride layer deposited over the memory stack and encapsulating the chalcogenide material, the silicon nitride layer deposited by alternating exposures of an iodine-containing silicon precursor and a second reactant using atomic layer deposition, the silicon nitride layer having a step coverage of between about 30% and about 90%; and a silicon-containing layer deposited directly on the silicon nitride layer by remote plasma chemical vapor deposition or plasma enhanced chemical vapor deposition at about 250° C., the silicon-containing layer having a wet etch rate of less than about 100 Å/minute using diluted hydrofluoric acid, wherein the hydrofluoric acid is diluted to a ratio of 100:1.

Another aspect involves a memory device including: a memory stack including a chalcogenide material; a silicon nitride layer deposited over the memory stack and encapsulating the chalcogenide material, the silicon nitride layer deposited by alternating exposures of a bromine-containing silicon precursor and a second reactant using atomic layer deposition, the silicon nitride layer having a step coverage of between about 30% and about 90%; and a silicon-containing layer deposited directly on the silicon nitride layer by remote plasma chemical vapor deposition or plasma enhanced chemical vapor deposition at about 250° C., the silicon-containing layer having a wet etch rate of less than about 100 Å/minute using diluted hydrofluoric acid, wherein the hydrofluoric acid is diluted to a ratio of 100:1.

These and other aspects are described further below with reference to the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of an example substrate.

FIG. 2A is a process flow diagram depicting operations for a method in accordance with disclosed embodiments.

FIG. 2B is a schematic illustration of an example substrate including layers deposited in accordance with certain disclosed embodiments.

FIG. 3 is a timing sequence diagram showing an example of cycles in a method in accordance with certain disclosed embodiments.

FIG. 4 is a schematic diagram of an example process chamber for performing disclosed embodiments.

FIG. 5 is a schematic diagram of an example process tool for performing disclosed embodiments.

FIG. 6A is an image of a substrate with silicon nitride deposited using certain disclosed embodiments.

FIG. 6B is a plot depicting an FTIR spectrum of experimental results for a silicon nitride film deposited using certain disclosed embodiments.

FIG. 7A is a plot of experimental results depicting the mole fraction composition of a GST (germanium, antimony, tellurium) substrate after exposure to ammonia plasma.

FIG. 7B is a plot of experimental results depicting the mole fraction composition of a GST (germanium, antimony, tellurium) substrate.

FIG. 7C is a plot of experimental results depicting the mole fraction composition of a GST (germanium, antimony, tellurium) substrate having a silicon nitride layer deposited using certain disclosed embodiments after exposure to ammonia plasma.

FIGS. 8A, 8B, and 8C are plots of experimental results depicting the mole fraction compositions of various GST substrates having silicon nitride deposited using certain disclosed embodiments to varying thicknesses after exposure to ammonia plasma.

DETAILED DESCRIPTION

In the following description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments.

Semiconductor fabrication processes often involve deposition of silicon nitride material. In one example, silicon nitride may be used in semiconductor device fabrication as diffusion barriers, gate insulators, sidewall spacers, and encapsulation layers. Conformal silicon nitride layers may also be used in other applications. For example, silicon nitride may be used during fabrication of memory structures. Conventional memory structures include metal oxide materials used for bit storage. However, as advanced memory structures are developed to accommodate smaller device sizes and improve efficiency, new challenges arise. Advanced memory architectures such as magnetoresistive random-access memory and phase change random-access memory (PCRAM) rely on new materials (other than metal oxides) for bit storage. In the case of PCRAM for example, the phase of a metal chalcogenide determines the bit state. Some example chalcogenides include sulfur (S), selenium (Se), and tellurium (Te). These new materials are air and moisture sensitive and may require encapsulation layers. When combined with appropriate metalloid ions such as germanium (Ge), antimony (Sb), etc., these chalcogenides form a phase change layer. If damaged, the phase change layer may not change phases. The phase change layer may also be sensitive to light. To prevent any damage to the phase change layer, a conformal silicon nitride memory encapsulation layer may be deposited over the phase change layer. The memory encapsulation layer has little to no contamination of other compounds and is deposited at low temperatures to avoid damaging the device.

However, many conventional deposition methods for depositing such silicon nitride layers as encapsulations layers for magnetic devices either deposit non-conformal films, such as in plasma enhanced chemical vapor deposition (PECVD), or use precursors that etch the chalcogenide material, such as by using a chlorine-containing or hydrogen-containing chemistry with plasma in atomic layer deposition (ALD). For example, the metal may undergo erosion as follows:

M_((solid))+xCl_((gas))→MCl_(x(gas))   Eqn. 1

In another example, the metal may undergo oxidation or nitridation. An example of an oxidation reaction may be as follows:

M_((solid))+xO_((gas))→MO_(x(solid))   Eqn. 2

Use of a chlorine-containing silicon precursor also often involves deposition at extremely high temperatures, such as at temperatures higher than about 500° C. As a result, deposition using chlorine-containing precursors has conventionally involved igniting a plasma to catalyze the reaction to form silicon nitride.

For example, some conventional deposition involves alternating doses of dichlorosilane (or another chlorine-containing precursor) and ammonia (NH₃) plasma, but both of these operations tend to generate species capable of etching chalcogenide material. For example, using dichlorosilane (SiCl₂H₂) as a silicon precursor for deposition of an encapsulation layer involves reacting dichlorosilane with a plasma to form the silicon nitride layer. However, when the plasma is ignited, dichlorosilane may be susceptible to forming hydrogen radicals and NH₂ radicals as well as hydrogen chloride, which may then attack metal chalcogenides and metal components of the chamber as shown in FIG. 1. Although chlorine-containing silicon precursors may be used to deposit films without a plasma, chlorine-containing silicon precursors are used at much higher temperatures (e.g., greater than 500° C.), and memory devices are susceptible to damage at these temperatures.

FIG. 1 depicts a substrate 100 including an oxide layer 101. The substrate 100 also includes a tungsten layer 103, carbon layer 105, chalcogenide layer 107, second carbon layer 115, second chalcogenide layer 117, third carbon layer 125, and nitride layer 109.

As shown in FIG. 1, if a chlorine-containing silicon precursor is used to deposit an encapsulation layer over the substrate, chlorine and/or hydrogen radicals generated when the plasma is ignited with the second reactant may react to form hydrogen chloride such that chlorine may react with aluminum, germanium, or antimony, or other chamber material metals including iron or copper. These materials (e.g., AlCl₃, GeCl₄, or SbCl₃) may generate an evaporative layer, which form volatile metal salts. These materials have a low boiling point; for example, the boiling point of AlCl₃ is 120° C., the boiling point of GeCl₄ is 87° C., and the boiling point of SbCl₃ is 200° C. These volatile metal salts may thereby redeposit onto other layers of the substrate resulting in defects and performance issues. Thus, chlorine precursors suffer from the general issues of metal contamination in the films due to chamber etching which produces volatile metal chlorides (Al, Fe, and Cu).

Similarly, a plasma generated from a nitrogen-containing reactant such as ammonia may form free hydrogen ions, radicals, and other plasma species that may also etch the chalcogenide. For example, a hydrogen plasma may react with tellurium or selenium to form H₂Te and H₂Se respectively, thereby removing material from the stack and resulting in performance issues and defects. These materials have a low boiling point; for example, H₂Te has a boiling point of −2° C., and H₂Se has a boiling point of −41° C. Generation of such material from exposure to hydrogen plasma may thereby etch the stack. Accordingly, conventional chlorine- and hydrogen-free processes (e.g. using an N₂ plasma) do not generate a conformal film and are not effective as barriers.

Provided herein are methods of encapsulating a chalcogenide material without damaging the chalcogenide. Methods involve deposition of silicon nitride using a chlorine-free iodine-containing and/or bromine-containing silicon precursor. By using a bromine-containing silicon precursor or bromosilane in place of a chlorine-containing silicon precursor, etching due to chlorine can be greatly reduced or eliminated. By using an iodine-containing silicon precursor or iodosilane in place of a chlorine-containing silicon precursor, etching due to chlorine can be greatly reduced or eliminated. Accordingly, in various embodiments described herein, a chlorine-free iodine-containing silicon precursor or chlorine-free bromine-containing silicon precursor is used for depositing a silicon nitride film. Iodine-containing and bromine-containing silicon precursors enable thermal deposition processes which further reduce etching due to free hydrogen present in the ammonia plasma used to make silicon nitride films. The terms “iodine-containing silicon precursor” and “iodosilane precursor” may be used interchangeably herein and both may refer to precursors including at least one silicon and at least one iodine atom. The terms “bromine-containing silicon precursor” and “bromosilane precursor” may be used interchangeably herein and both may refer to precursors including at least one silicon and at least one bromine atom. Materials generated from reacting an iodosilane precursor with the metals described herein have higher boiling points than materials generated when reacted with a chlorosilane. For example, materials generated from reacting an iodosilane precursor with aluminum have a boiling point greater than 240° C., materials generated from reacting an iodosilane precursor with germanium have a boiling point greater than 353° C., and materials generated from reacting an iodosilane precursor with antimony have boiling points greater than 181° C. Bromosilane precursors are expected to be more volatile than iodosilane precursors due to their lower boiling points. However, surprisingly, bromosilanes precursors behave similar to that of iodosilane and are effective in forming hermetic, conformal, non-damaging encapsulation layers. Encapsulation layers described herein are hermetic, conformal, and non-damaging and may be deposited at low temperatures such as temperatures less than about 300° C. For example, in some embodiments, disclosed embodiments are performed at a temperature between about 50° C. and about 300° C., such as at a temperature between about 200° C. and about 275° C. In some embodiments, silicon nitride is deposited at a temperature between about 50° C. and about 300° C. In some embodiments, silicon nitride is deposited at a temperature between about 200° C. and about 275° C. In some embodiments, encapsulation layers are deposited using certain disclosed embodiments at temperatures greater than or equal to about 250° C.

The deposited films are conformal. Conformality of films may be measured by the step coverage. “Step coverage” as used herein is calculated by dividing the average thickness of the deposited film on the sidewall by the average thickness of the deposited film at the top of the feature and multiplying it by 100 to obtain a percentage. Disclosed embodiments may deposit films having a step coverage of at least about 95%, or about 100%, or 100%. In some embodiments, substrates include stacks whereby an aspect ratio between stacks is about 5:1, and disclosed embodiments may deposit silicon nitride to a step coverage of at least about 95% using an iodine-containing precursor and ammonia. In some embodiments, the presence of some hydrogen in the plasma or second reactant may improve film conformality.

As compared to conventional chlorine-containing chemistries, disclosed embodiments may be more compatible with various materials as shown in Table 1 below. Although some H₂ may be formed if a NH₃ plasma is used to generate H₂Te, disclosed embodiments are generally suitable for various materials using low or no H₂ exposure. Disclosed embodiments also exhibit little to no pattern loading sensitivity.

TABLE 1 Material Compatibility Chlorine-containing Iodine-containing Bromine-containing Material Chemistry Chemistry Chemistry As Not Compatible Compatible Compatible Ge Only Compatible with Compatible Compatible <250° C. Compounds Sb Only Compatible with Compatible Compatible <250° C. Compounds Te Compatible Compatible Compatible Se Only Compatible with Compatible Compatible <250° C. Compounds

Embodiments described herein involve deposition by ALD. ALD is a technique that deposits thin layers of material using sequential self-limiting reactions. Typically, an ALD cycle includes operations to deliver and adsorb at least one reactant to the substrate surface, and then react the adsorbed reactant with one or more reactants to form the partial layer of film. As an example, a silicon nitride deposition cycle may include the following operations: (i) delivery/adsorption of an iodine-containing silicon precursor, (ii) purging of the iodine-containing silicon precursor from the chamber, (iii) delivery of a nitrogen-containing reactant with an optional plasma, and (iv) purging of the nitrogen-containing gas and/or plasma from the chamber.

Unlike a chemical vapor deposition (CVD) technique, ALD processes use surface-mediated deposition reactions to deposit films on a layer-by-layer basis. In one example of an ALD process, a substrate surface that includes a population of surface active sites is exposed to a gas phase distribution of a first precursor, such as an iodine-containing or bromine-containing silicon precursor, in a dose provided to a chamber housing a substrate. Molecules of this first precursor are adsorbed onto the substrate surface, including chemisorbed species and/or physisorbed molecules of the first precursor. It should be understood that when the compound is adsorbed onto the substrate surface as described herein, the adsorbed layer may include the compound as well as derivatives of the compound. For example, an adsorbed layer of an iodine-containing silicon precursor may include the iodine-containing silicon precursor as well as derivatives of the iodine-containing silicon precursor. After a first precursor dose, the chamber is then evacuated to remove most or all of first precursor remaining in gas phase so that mostly or only the adsorbed species remain. In some implementations, the chamber may not be fully evacuated. For example, the chamber may be evacuated such that the partial pressure of the first precursor in gas phase is sufficiently low to mitigate a reaction. A second reactant, such as a nitrogen-containing reactant, is introduced to the chamber so that some of these molecules react with the first precursor adsorbed on the surface. In some processes, the second precursor reacts immediately with the adsorbed first precursor. In other embodiments, the second reactant reacts only after a source of activation is applied temporally. In some embodiments, a plasma is ignited during the second reactant dose. The chamber may then be evacuated again to remove unbound second reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness.

In certain embodiments, an ALD first precursor dose partially saturates the substrate surface. In some embodiments, the dose phase of an ALD cycle concludes before the precursor contacts the substrate to evenly saturate the surface. Typically, the precursor flow is turned off or diverted at this point, and only purge gas flows. By operating in this sub-saturation regime, the ALD process reduces the cycle time and increases throughput. However, because precursor adsorption is not saturation limited, the adsorbed precursor concentration may vary slightly across the substrate surface. Examples of ALD processes operating in the sub-saturation regime are provided in U.S. patent application Ser. No. 14/061,587 (now U.S. Pat. No. 9,355,839), filed Oct. 23, 2013, titled “SUB-SATURATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILM DEPOSITION,” which is incorporated herein by reference in its entirety.

As described, in some implementations, the ALD methods include plasma activation. As described herein, the ALD methods and apparatuses described herein may be conformal film deposition (CFD) methods, which are described generally in U.S. patent application Ser. No. 13/084,399 (now U.S. Pat. No. 8,728,956), filed Apr. 11, 2011, and titled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION,” and in U.S. patent application Ser. No. 13/084,305, filed Apr. 11, 2011, and titled “SILICON NITRIDE FILMS AND METHODS,” which are herein incorporated by reference in their entireties.

FIG. 2A shows a process flow diagram depicting example operations of disclosed embodiments. In operation 201, a substrate is provided to a process chamber. The substrate may be a silicon wafer, e.g., a 200-mm wafer, a 300-mm wafer, or a 450-mm wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semi-conducting material deposited thereon. Non-limiting examples of under-layers include dielectric layers and conducting layers, e.g., silicon oxides, silicon nitrides, silicon carbides, metal oxides, metal nitrides, metal carbides, and metal layers. In some embodiments, the substrate includes a stack such as the one depicted in FIG. 1. In some embodiments, the substrate includes two or more stacks, each of the stacks including layers such as the layers depicted in FIG. 1. The space between stacks may be narrow such that aspect ratios between stacks may be between about 3:1 and about 10:1, such as about 5:1.

During operations 203-215 of FIG. 2A, an inert gas may be flowed. In various embodiments, the inert gas is used as a carrier gas. Example carrier gases include argon, helium, and neon. In some embodiments, a hydrogen-containing carrier gas may be used. In some embodiments, the carrier gas is used as a purge gas in some operations. In some embodiments, the carrier gas is diverted. The inert gas may be provided to assist with pressure and/or temperature control of the process chamber, evaporation of a liquid reactant, more rapid delivery of the reactant and/or as a sweep gas for removing process gases from the process chamber and/or process chamber plumbing.

Various disclosed embodiments may be performed at a pressure between about 0.1 Torr and about 20 Torr. In many embodiments, the methods disclosed may be performed at a substrate temperature less than about 300° C., such as between about 50° C. and about 300° C., for example, about 250° C. In such embodiments, the pedestal may be set to a temperature of less than about 300° C. to control the substrate temperature. For example, for MRAM and PCRAM applications, the materials on the substrate may be sensitive to high temperatures. In some embodiments, disclosed embodiments are performed at a temperature between about 50° C. and about 300° C., such as at a temperature between about 200° C. and about 275° C. In some embodiments, silicon nitride is deposited at a temperature between about 50° C. and about 300° C. In some embodiments, silicon nitride is deposited at a temperature between about 200° C. and about 275° C.

In operation 203, the substrate is exposed to an iodine-containing and/or bromine-containing silicon precursor such that the iodine-containing and/or bromine-containing silicon precursor adsorbs onto the substrate surface. Iodine-containing and/or bromine-containing silicon precursors may be completely substituted with bromine and/or iodine atoms in various embodiments. That is, iodine-containing precursors and/or bromine-containing precursors may have no hydrogen atoms. Disclosed embodiments involve precursors not conventionally used for deposition of silicon nitride by ALD. Using an iodine-containing and/or bromine-containing silicon precursor allows for chlorine-free deposition. Example iodine-containing silicon precursors include diiodosilane (DIS), tetraiodosilane, hexaiododisilane, and others. In various embodiments, bromine-containing silicon precursors are fully halogenated. Bromine-containing silicon precursors may have the chemical formula Si_(x)Br_(y)I_(z), where if x=1, y is an integer between and including 1 and 4, and y+z=4, or where if x=2, y is an integer between and including 1 and 6, and y+z=6. Example bromine-containing silicon precursors include tetrabromosilane (SiBr₄), SiBr₃I, SiBr₂I₂, SiBrI₃, hexabromodisilane (Si₂Br₆), Si₂Br₅I, Si₂Br₄I₂, Si₂Br₃I₃, Si₂Br₂I₄, Si₂BrI₅, and combinations thereof.

Operation 203 may be part of an ALD cycle. As discussed above, generally an ALD cycle is the minimum set of operations used to perform a surface deposition reaction one time. In some embodiments, the result of one cycle is production of at least a partial silicon nitride film layer on a substrate surface. The cycle may include certain ancillary operations such as sweeping one of the reactants or byproducts and/or treating the partial film as deposited. Generally, a cycle contains one instance of a unique sequence of operations. As discussed above, generally a cycle is the minimum set of operations used to perform a surface deposition reaction one time. The result of one cycle is production of at least a partial film layer, e.g., a partial silicon nitride film layer, on a substrate surface.

During operation 203, the substrate is exposed to the first precursor such that the first precursor is adsorbed onto the substrate surface to form an adsorbed layer. In some embodiments, an iodine-containing and/or bromine-containing silicon precursor adsorbs onto the substrate surface in a self-limiting manner such that once active sites are occupied by the iodine-containing and/or bromine-containing silicon precursor, little or no additional iodine-containing and/or bromine-containing silicon precursor will be adsorbed on the substrate surface. For example, iodine-containing and/or bromine-containing silicon precursor may be adsorbed onto about 60% of the substrate surface. In various embodiments, when the iodine-containing and/or bromine-containing silicon precursor is flowed to the chamber, the iodine-containing and/or bromine-containing silicon precursor adsorbs onto active sites on the surface of the substrate, forming a thin layer of the iodine-containing and/or bromine-containing silicon precursor on the surface. In various embodiments, this layer may be less than a monolayer, and may have a thickness between about 0.2 Å and about 0.4 Å. Methods provided herein may be performed at a temperature less than about 300° C., such as at about 250° C. In some embodiments, disclosed embodiments are performed at a temperature between about 50° C. and about 300° C., such as at a temperature between about 200° C. and about 275° C. In some embodiments, silicon nitride is deposited at a temperature between about 50° C. and about 300° C. In some embodiments, silicon nitride is deposited at a temperature between about 200° C. and about 275° C.

In operation 205, the process chamber is optionally purged to remove excess iodine-containing silicon precursor in gas phase that did not adsorb onto the surface of the substrate. Purging the chamber may involve flowing a purge gas or a sweep gas, which may be a carrier gas used in other operations or may be a different gas. In some embodiments, purging may involve evacuating the chamber. Example purge gases include argon, nitrogen, hydrogen, and helium. In some embodiments, operation 205 may include one or more evacuation subphases for evacuating the process chamber. Alternatively, it will be appreciated that operation 205 may be omitted in some embodiments. Operation 205 may have any suitable duration, such as between about 0 seconds and about 60 seconds, for example about 0.01 seconds. In some embodiments, increasing a flow rate of one or more purge gases may decrease the duration of operation 205. For example, a purge gas flow rate may be adjusted according to various reactant thermodynamic characteristics and/or geometric characteristics of the process chamber and/or process chamber plumbing for modifying the duration of operation 205. In one non-limiting example, the duration of a purge phase may be adjusted by modulating purge gas flow rate. This may reduce deposition cycle time, which may improve substrate throughput. After a purge, the iodine-containing and/or bromine-containing silicon precursors remain adsorbed onto the substrate surface.

In operation 211, the substrate is exposed to a second reactant to react with the adsorbed layer of the iodine-containing and/or bromine-containing silicon precursor. Note that the term “second reactant” may be used to describe one or more gases introduced to the chamber when plasma is ignited in an ALD cycle.

In some embodiments, the reaction may be thermal. Methods involving thermal ALD using either ammonia (NH₃) or hydrazines (e.g., H₄N₂) reduce contamination and reduce the presence of hydrogen radicals during deposition, thereby reducing etching of the chalcogenide and/or metals on the substrate and/or in the chamber. For a thermal process, deposition may be performed at a temperature of at least about 250° C., such as about 300° C. In some embodiments, disclosed embodiments are performed at a temperature between about 50° C. and about 300° C., such as at a temperature between about 200° C. and about 275° C. In some embodiments, silicon nitride is deposited at a temperature between about 50° C. and about 300° C. In some embodiments, silicon nitride is deposited at a temperature between about 200° C. and about 275° C.

In some embodiments, a plasma may be optionally ignited in operation 211. Plasma energy may be provided to activate the second reactant, such as a nitrogen-containing gas, into ions and radicals and other activated species, which react with the adsorbed layer of the first precursor. In disclosed embodiments involving a plasma, the plasma may include less than about 1% hydrogen radicals, thereby reducing etching of chalcogenide or metal material during deposition. In various embodiments, the plasma is an in-situ plasma, such that the plasma is formed directly above the substrate surface in the chamber. The in-situ plasma may be ignited at a power per substrate area between about 0.2122 W/cm² and about 2.122 W/cm². For example, the power may range from about 150 W to about 6000 W, or from about 600 W to about 6000 W, or from about 800 W to about 4000 W, for a chamber processing four 300 mm wafers. For example, plasmas for ALD processes may be generated by applying a radio frequency (RF) field to a gas using two capacitively coupled plates. Ionization of the gas between plates by the RF field ignites the plasma, creating free electrons in the plasma discharge region. These electrons are accelerated by the RF field and may collide with gas phase reactant molecules. Collision of these electrons with reactant molecules may form radical species that participate in the deposition process. It will be appreciated that the RF field may be coupled via any suitable electrodes. In various embodiments, a high frequency plasma is used having a frequency of at least about 13.56 MHz, or at least about 27 MHz, or at least about 40 MHz, or at least about 60 MHz. In some embodiments, a microwave-based plasma may be used. Non-limiting examples of electrodes include process gas distribution showerheads and substrate support pedestals. It will be appreciated that plasmas for ALD processes may be formed by one or more suitable methods other than capacitive coupling of an RF field to a gas. In some embodiments, the plasma is a remote plasma, such that a second reactant is ignited in a remote plasma generator upstream of the chamber, then delivered to the chamber where the substrate is housed.

Where a plasma is used, a dose of an iodine-containing silicon precursor may be followed by a dose of nitrogen (N₂) or hydrogen (H₂) plasma. The corresponding iodine-containing and/or bromine-containing metal salts that may generate from reacting with chalcogenides on the substrate or metals of the chamber components may not be sufficiently volatile to result in wafer contamination. For example, iodine-containing salts including aluminum, germanium, or antimony have higher boiling points than corresponding chlorine-containing salts. As a result, iodine-containing salts may form a passivation layer, but not an evaporative layer, and the salts are less likely to redeposit onto materials on the substrate. In some cases, aluminum may react with chlorine such that the chamber is etched and therefore damaged, and aluminum may also decompose onto the wafer.

Returning to FIG. 2A, in operation 213, the chamber is optionally purged to remove the etched species and any residual byproducts. Operation 213 may be purged using any of the conditions described above with respect to operation 205.

In operation 215 of FIG. 2A, it is determined whether the desired thickness of film has been deposited. If not, operations 203-213 are repeated in sufficient cycles to deposit a desired thickness of film. Any suitable number of deposition cycles may be included in an ALD process to deposit a desired film thickness of silicon nitride. For example, about fifty deposition cycles may be performed to deposit a film on the substrate using disclosed embodiments. In some embodiments the thickness of the deposited silicon nitride film may be greater than about 30 Å on a sidewall over a stack of films for fabrication of a memory device.

Disclosed embodiments may be used for various applications. One application may include encapsulating chalcogenides using a bilayer film to achieve a low wet etch rate. In various deposition processes, it may be desired to achieve advanced memory architectures that also have good adhesion to underlayers, absence of hydrogen radicals, low wet etch rate (WER), tight across-wafer uniformity, ability to fill high aspect ratio features as well as low thermal conductivity from line to line. While conventional deposition techniques may not achieve these characteristics within a single film, disclosed embodiments may be suitable for depositing films having such characteristics.

The Joule heat generated inside a MRAM or PCRAM device may determine the switching behavior of the device, and for high density memory arrays, the temperature surrounding may lead to a consequent resistance degradation of neighboring devices during cycling. Conventional films are unlikely to meet the above specifications and limit thermal cross talk. Pulsed plasma (e.g., plasma-enhanced chemical vapor deposition) may be used for some applications but may result in low device yield and is incapable of being extended to the next node which will have even more aggressive features.

Disclosed embodiments may be used to deposit a bilayer film capable of achieving the above described characteristics. A dense, low WER film can protect the encapsulation layer from being etched in subsequent processing, such as by polishing. A bilayer film may be deposited whereby the first layer is a uniform, conformal ALD SiN layer with good air and moisture barrier with little or no hydrogen radicals, and a top layer is a low wet etch rate film. In some embodiments, the first layer may be a silicon nitride layer deposited using an iodine-containing silicon precursor as described above with respect to FIG. 2A. In various embodiments, the second or top layer may reduce lateral conduction by having two interfaces. Disclosed embodiments may use the combination of properties from two or more films. One or more of these films may be deposited by a remote plasma chemical vapor deposition (RPCVD) process. In some embodiments, one or more of these films may be deposited by plasma enhanced chemical vapor deposition (PECVD).

In various embodiments, a first layer may have superior step coverage, low or no hydrogen radicals or ions, and good adhesion to underlayers. In some embodiments, the first layer may have step coverage of up to about 100% for features having an aspect ratio of about 13:1. In some embodiments, the first layer may also be a non-oxidizing film. A non-oxidizing film may be advantageous to reducing damage to the underlying substrate.

A second layer may have superior wet etch performance. For example, in some embodiments, the wet etch rate may be less than about 100 Å per minute or less than about 10 Å per minute in diluted hydrofluoric acid, where hydrofluoric acid is diluted to a ratio of 100:1. The second layer may include silicon nitride, silicon carbide, silicon carbonitride, silicon oxycarbide, or combinations thereof. The film may be hermetic. In some embodiments, the second layer has low hydrogen desorption. Without being bound by a particular theory, the second layer having low hydrogen desorption may be less susceptible to releasing hydrogen, thereby increasing thermal stability and reducing the likelihood of etching or damaging the substrate during deposition. In some embodiments, the second layer has a step coverage of between about 60% and about 90% for features having an aspect ratio of about 4:1.

In various embodiments, the second layer is deposited such that it forms a non-conformal breadloaf at or near the top of the features. For example, in some embodiments, the second layer is deposited such that the sidewall thickness is greater at the top than at the bottom of a feature.

In various embodiments, the second layer may be a silicon carbide or a silicon nitride film deposited by PECVD. In some embodiments, the second layer may be deposited by pulsed PECVD. In some embodiments, the second layer may be deposited by non-pulsed PECVD. The second layer as deposited by PECVD may include high silicon content. In some embodiments, the first and second layers are deposited in the same chamber or module. In some embodiments, the first and second layers are deposited without an air break.

FIG. 2B shows an example of a substrate 290 including an oxide layer 241. The substrate 290 includes two memory stacks. One stack includes a tungsten layer 243 a, carbon layer 245 a, chalcogenide layer 247 a, second carbon layer 255 a, second chalcogenide layer 257 a, third carbon layer 265 a, and a nitride layer 249 a. The second stack includes a tungsten layer 243 b, carbon layer 245 b, chalcogenide layer 247 b, second carbon layer 255 b, second chalcogenide layer 257 b, third carbon layer 265 b, and a nitride layer 249 b. Both stacks include nitride spacers 289 and a silicon-containing film 299 is deposited over the substrate such that the film breadloafs at the top of the feature. The silicon-containing film 299 may be a silicon nitride film, or a silicon carbide film, or a silicon carbon-containing film such as SiCN or SiOC film.

As shown, the silicon-containing film 299 may also be created to form a non-conformal breadloaf at the top, which leaves a void 240 between the stacks and thus an added thermal barrier between the stacks. Breadloafing as described herein may include non-conformal coverage having a step coverage between about 30% and about 90%, or between about 50% and about 90%. The silicon-containing film 299 may be deposited such that the sidewall thickness is greater at the top than at the bottom of a feature. In some embodiments, the deposited film may be deposited non-conformally such that deposition thickness at or near the top of the stacks is at least between about 10% and about 50% thicker than deposition thickness on the sidewalls and/or on the substrate between stacks. Breadloafing results in more deposition at or near the top of the stacks such that the film is deposited thicker at or near the top of the stacks, while deposition thickness in between the stacks (on the sidewalls and on the bottom of the gap between the stacks) is thinner. As a result of this non-conformal deposition, a void is formed between stacks because the thicker deposition at or near the top of the stacks prevents further deposition into the feature, thereby forming a void between the sidewalls. While non-conformal top-heavy deposition is usually avoided, in this case, such deposition techniques may be beneficial. FIG. 2B shows an example substrate where there may be more deposition at or near the top of the features between lines to form the breadloaf thereby forming a void 240 between two lines.

As described above, films may be deposited at low temperature. Additional descriptions for deposition of silicon-containing carbon-containing films such as SiC and SiOC using a remote plasma chemical vapor deposition (RPCVD) apparatus are further described in U.S. patent application Ser. No. 13/907,699 (Attorney Docket No. LAMRP046) filed on May 31, 2013 entitled “METHOD TO OBTAIN SIC CLASS OF FILMS OF DESIRED COMPOSITION AND FILM PROPERTIES” and issued as U.S. Pat. No. 9,234,276 on Jan. 12, 2016; U.S. patent application Ser. No. 13/494,836 (Attorney Docket No. NOVLP466) filed on Jun. 21, 2012 entitled “REMOTE PLASMA BASED DEPOSITION OF SiOC CLASS OF FILMS”; U.S. patent application Ser. No. 14/616,435 filed on Feb. 6, 2015 entitled “CONFORMAL DEPOSITION OF SILICON CARBIDE FILMS” (Attorney Docket No. LAMRP175); and U.S. patent application Ser. No. 14/712,167 filed on May 14, 2015 entitled “MINIMIZING RADICAL RECOMBINATION USING ALD SILICON OXIDE SURFACE COATING WITH INTERMITTENT RESTORATION PLASMA” (Attorney Docket No. LAMRP169), which are all herein incorporated by reference in their entireties.

FIG. 3 is a timing sequence diagram of example pulses in accordance with disclosed embodiments. FIG. 3 shows phases in an example ALD process 300, for various process parameters, such as carrier gas or purge gas flow, iodosilane and/or bromosilane precursor flow, and second reactant flow. The lines indicate when the flow is turned on and off. Note that the example provided in FIG. 3 does not include turning off and on a plasma, but in various embodiments, a plasma may be used to generate plasma with the second reactant gas. Example process parameters include, but are not limited to, flow rates for inert and reactant species, substrate temperature, and process chamber pressure.

Two deposition cycles 310A and 310B are depicted. Each deposition cycle includes various phases. For example, deposition cycle 310A includes an iodine-containing silicon precursor (indicated as iodosilane in FIG. 3) and/or bromine-containing silicon precursor (indicated as bromosilanes in FIG. 3) exposure phase 357A, a purge phase 359A, a second reactant (e.g., nitrogen reactant) exposure phase 361A, and a purge phase 363A. Likewise, deposition cycle 310B an iodine-containing and/or bromine-containing silicon precursor exposure phase 357B, another purge phase 359B, a nitrogen reactant exposure phase 361B, and a purge phase 363B. As shown, in example process 300, a carrier gas is flowed throughout the deposition cycles 310A and 310B. In various embodiments, the carrier gas is used as a purge gas. In some embodiments, the carrier gas may be different than the purge gas. In some embodiments, a carrier gas is only flowed during purge phases (e.g., 359A, 363A, 359B, and 363B). A carrier gas may be any of those described above with respect to FIG. 2A.

In iodine-containing silicon precursor exposure phase 357A, the iodine-containing and/or bromine-containing silicon precursor flow and carrier gas flow are turned on while the nitrogen reactant flow is turned off. This may correspond to operation 203 of FIG. 2A. In purge phase 359A, the carrier gas flow is turned on, while the iodine-containing and/or bromine-containing silicon precursor flow, and nitrogen reactant flow are turned off. This may correspond to operation 205 of FIG. 2A. In nitrogen reactant exposure phase 361A, the carrier gas flow and nitrogen reactant flow are turned on while the iodine-containing and/or bromine-containing silicon precursor flow is turned off. Note that in some embodiments, depending on the nitrogen reactant chosen and process conditions, the plasma may be turned on during this phase. This phase may correspond to operation 211 of FIG. 2A. Returning to FIG. 3, in purge phase 363A, the carrier gas flow is turned on, while the iodine-containing and/or bromine-containing silicon precursor flow, and nitrogen reactant flow are turned off. Note that as shown in FIG. 3, these phases may then be repeated in deposition cycle 310B upon determining in operation 215 of FIG. 2A that the film has not been deposited to an adequate thickness. Accordingly, deposition cycle 310B may then include an iodine-containing and/or bromine-containing silicon precursor exposure phase 357B, followed by a purge phase 359B, a nitrogen reactant exposure phase 361B, and a subsequent purge phase 363B. These phases as shown in FIG. 3 may have the same pattern of corresponding flows for carrier gas, iodine-containing and/or bromine-containing silicon precursor gas, and nitrogen reactant gas flow as in deposition cycle 310A.

APPARATUS

FIG. 4 depicts a schematic illustration of an embodiment of an atomic layer deposition (ALD) process station 400 having a process chamber body 402 for maintaining a low-pressure environment. A plurality of ALD process stations 400 may be included in a common low pressure process tool environment. For example, FIG. 5 depicts an embodiment of a multi-station processing tool 500. In some embodiments, one or more hardware parameters of ALD process station 400 including those discussed in detail below may be adjusted programmatically by one or more computer controllers 450.

ALD process station 400 fluidly communicates with reactant delivery system 401 a for delivering process gases to a distribution showerhead 406. Reactant delivery system 401 a includes a mixing vessel 404 for blending and/or conditioning process gases, such as an iodine-containing and/or bromine-containing silicon precursor gas, or second reactant gas (e.g., ammonia or hydrazine), for delivery to showerhead 406. One or more mixing vessel inlet valves 420 may control introduction of process gases to mixing vessel 404. Nitrogen plasma or hydrogen plasma may also be delivered to the showerhead 406 or may be generated in the ALD process station 400.

As an example, the embodiment of FIG. 4 includes a vaporization point 403 for vaporizing liquid reactant to be supplied to the mixing vessel 404. In some embodiments, vaporization point 403 may be a heated vaporizer. The saturated reactant vapor produced from such vaporizers may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactant may create small particles. These small particles may clog piping, impede valve operation, contaminate substrates, etc. Some approaches to addressing these issues involve purging and/or evacuating the delivery piping to remove residual reactant. However, purging the delivery piping may increase process station cycle time, degrading process station throughput. Thus, in some embodiments, delivery piping downstream of vaporization point 403 may be heat traced. In some examples, mixing vessel 404 may also be heat traced. In one non-limiting example, piping downstream of vaporization point 403 has an increasing temperature profile extending from approximately 100° C. to approximately 150° C. at mixing vessel 404.

In some embodiments, liquid precursor or liquid reactant may be vaporized at a liquid injector. For example, a liquid injector may inject pulses of a liquid reactant into a carrier gas stream upstream of the mixing vessel. In one embodiment, a liquid injector may vaporize the reactant by flashing the liquid from a higher pressure to a lower pressure. In another example, a liquid injector may atomize the liquid into dispersed microdroplets that are subsequently vaporized in a heated delivery pipe. Smaller droplets may vaporize faster than larger droplets, reducing a delay between liquid injection and complete vaporization. Faster vaporization may reduce a length of piping downstream from vaporization point 403. In one scenario, a liquid injector may be mounted directly to mixing vessel 404. In another scenario, a liquid injector may be mounted directly to showerhead 406.

In some embodiments, a liquid flow controller (LFC) upstream of vaporization point 403 may be provided for controlling a mass flow of liquid for vaporization and delivery to process station 400. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC may then be adjusted responsive to feedback control signals provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it may take one second or more to stabilize liquid flow using feedback control. This may extend a time for dosing a liquid reactant. Thus, in some embodiments, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this may be performed by disabling a sense tube of the LFC and the PID controller.

Showerhead 406 distributes process gases toward substrate 412. In the embodiment shown in FIG. 4, the substrate 412 is located beneath showerhead 406 and is shown resting on a pedestal 408. Showerhead 406 may have any suitable shape, and may have any suitable number and arrangement of ports for distributing process gases to substrate 412.

In some embodiments, pedestal 408 may be raised or lowered to expose substrate 412 to a volume between the substrate 412 and the showerhead 406. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller 450.

In another scenario, adjusting a height of pedestal 408 may allow a plasma density to be varied during plasma activation cycles in the process in embodiments where a plasma is ignited. At the conclusion of the process phase, pedestal 408 may be lowered during another substrate transfer phase to allow removal of substrate 412 from pedestal 408.

In some embodiments, pedestal 408 may be temperature controlled via heater 410. In some embodiments, the pedestal 408 may be heated to a temperature of at least about 250° C., or in some embodiments, less than about 300° C., such as about 250° C., during deposition of silicon nitride films as described in disclosed embodiments. In some embodiments, the pedestal is set at a temperature between about 50° C. and about 300° C., such as at a temperature between about 200° C. and about 275° C. In some embodiments, the pedestal is set at a temperature between about 50° C. and about 300° C. In some embodiments, the pedestal is set at a temperature between about 200° C. and about 275° C.

Further, in some embodiments, pressure control for process station 400 may be provided by butterfly valve 418. As shown in the embodiment of FIG. 4, butterfly valve 418 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of process station 400 may also be adjusted by varying a flow rate of one or more gases introduced to the process station 400.

In some embodiments, a position of showerhead 406 may be adjusted relative to pedestal 408 to vary a volume between the substrate 412 and the showerhead 406. Further, it will be appreciated that a vertical position of pedestal 408 and/or showerhead 406 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, pedestal 408 may include a rotational axis for rotating an orientation of substrate 412. It will be appreciated that, in some embodiments, one or more of these example adjustments may be performed programmatically by one or more suitable computer controllers 450.

In some embodiments where plasma may be used as discussed above, showerhead 406 and pedestal 408 electrically communicate with a radio frequency (RF) power supply 414 and matching network 416 for powering a plasma. In some embodiments, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 414 and matching network 416 may be operated at any suitable power to form a plasma having a desired composition of radical species. Examples of suitable powers are included above. Likewise, RF power supply 414 may provide RF power of any suitable frequency. In some embodiments, RF power supply 414 may be configured to control high- and low-frequency RF power sources independently of one another. Example low-frequency RF frequencies may include, but are not limited to, frequencies between 0 kHz and 500 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz, or greater than about 13.56 MHz, or greater than 27 MHz, or greater than 40 MHz, or greater than 60 MHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions.

In some embodiments, the plasma may be monitored in-situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, plasma density and/or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, an OES sensor may be used in a feedback loop for providing programmatic control of plasma power. It will be appreciated that, in some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

In some embodiments, instructions for a controller 450 may be provided via input/output control (IOC) sequencing instructions. In one example, the instructions for setting conditions for a process phase may be included in a corresponding recipe phase of a process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a process phase are executed concurrently with that process phase. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe phase. For example, a first recipe phase may include instructions for setting a flow rate of an inert and/or a reactant gas (e.g., the first precursor such as an iodine-containing and/or bromine-containing silicon precursor), instructions for setting a flow rate of a carrier gas (such as argon), and time delay instructions for the first recipe phase. A second, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and/or a reactant gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the second recipe phase. A third recipe phase may include instructions for modulating a flow rate of a second reactant gas such as ammonia, instructions for modulating the flow rate of a carrier or purge gas, and time delay instructions for the third recipe phase. A fourth, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and/or a reactant gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the fourth recipe phase. It will be appreciated that these recipe phases may be further subdivided and/or iterated in any suitable way within the scope of the disclosed embodiments. In some embodiments, the controller 450 may include any of the features described below with respect to system controller 550 of FIG. 5.

As described above, one or more process stations may be included in a multi-station processing tool. FIG. 5 shows a schematic view of an embodiment of a multi-station processing tool 500 with an inbound load lock 502 and an outbound load lock 504, either or both of which may include a remote plasma source. A robot 506 at atmospheric pressure is configured to move wafers from a cassette loaded through a pod 508 into inbound load lock 502 via an atmospheric port 510. A wafer is placed by the robot 506 on a pedestal 512 in the inbound load lock 502, the atmospheric port 510 is closed, and the load lock is pumped down. Where the inbound load lock 502 includes a remote plasma source, the wafer may be exposed to a remote plasma treatment in the load lock prior to being introduced into a processing chamber 514. Further, the wafer also may be heated in the inbound load lock 502 as well, for example, to remove moisture and adsorbed gases. Next, a chamber transport port 516 to processing chamber 514 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal of a first station shown in the reactor for processing. While the embodiment depicted in FIG. 5 includes load locks, it will be appreciated that, in some embodiments, direct entry of a wafer into a process station may be provided.

The depicted processing chamber 514 includes four process stations, numbered from 1 to 4 in the embodiment shown in FIG. 5. Each station has a heated pedestal (shown at 518 for station 1), and gas line inlets. It will be appreciated that in some embodiments, each process station may have different or multiple purposes. For example, in some embodiments, a process station may be switchable between an ALD and plasma-enhanced ALD process mode. Additionally or alternatively, in some embodiments, processing chamber 514 may include one or more matched pairs of ALD and plasma-enhanced ALD process stations. While the depicted processing chamber 514 includes four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments a processing chamber may have three or fewer stations.

FIG. 5 depicts an embodiment of a wafer handling system for transferring wafers within processing chamber 514. In some embodiments, wafer handling system may transfer wafers between various process stations and/or between a process station and a load lock. It will be appreciated that any suitable wafer handling system may be employed. Non-limiting examples include wafer carousels and wafer handling robots. FIG. 5 also depicts an embodiment of a system controller 550 employed to control process conditions and hardware states of process tool 500. System controller 550 may include one or more memory devices 556, one or more mass storage devices 554, and one or more processors 552. Processor 552 may include a CPU or computer, analog, and/or digital input/output connections, stepper motor controller boards, etc.

In some embodiments, system controller 550 controls all of the activities of process tool 500. System controller 550 executes system control software 558 stored in mass storage device 554, loaded into memory device 556, and executed on processor 552. Alternatively, the control logic may be hard coded in the controller 550. Applications Specific Integrated Circuits, Programmable Logic Devices (e.g., field-programmable gate arrays, or FPGAs) and the like may be used for these purposes. In the following discussion, wherever “software” or “code” is used, functionally comparable hard coded logic may be used in its place. System control software 558 may include instructions for controlling the timing, mixture of gases, gas flow rates, chamber and/or station pressure, chamber and/or station temperature, wafer temperature, target power levels, RF power levels, substrate pedestal, chuck and/or susceptor position, and other parameters of a particular process performed by process tool 500. System control software 558 may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components used to carry out various process tool processes. System control software 558 may be coded in any suitable computer readable programming language.

In some embodiments, system control software 558 may include input/output control (IOC) sequencing instructions for controlling the various parameters described above. Other computer software and/or programs stored on mass storage device 554 and/or memory device 556 associated with system controller 550 may be employed in some embodiments. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

A substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal 518 and to control the spacing between the substrate and other parts of process tool 500.

A process gas control program may include code for controlling gas composition (e.g., iodine-containing silicon precursor gases, and nitrogen-containing gases, carrier gases and purge gases as described herein) and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. A pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc.

A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate.

A plasma control program may include code for setting RF power levels applied to the process electrodes in one or more process stations in accordance with the embodiments herein.

A pressure control program may include code for maintaining the pressure in the reaction chamber in accordance with the embodiments herein.

In some embodiments, there may be a user interface associated with system controller 550. The user interface may include a display screen, graphical software displays of the apparatus and/or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

In some embodiments, parameters adjusted by system controller 550 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels), etc. These parameters may be provided to the user in the form of a recipe, which may be entered utilizing the user interface.

Signals for monitoring the process may be provided by analog and/or digital input connections of system controller 550 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of process tool 500. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

System controller 550 may provide program instructions for implementing the above-described deposition processes. The program instructions may control a variety of process parameters, such as DC power level, RF bias power level, pressure, temperature, etc. The instructions may control the parameters to operate in-situ deposition of film stacks according to various embodiments described herein.

The system controller 550 will typically include one or more memory devices and one or more processors configured to execute the instructions so that the apparatus will perform a method in accordance with disclosed embodiments. Machine-readable media containing instructions for controlling process operations in accordance with disclosed embodiments may be coupled to the system controller 550.

In some implementations, the system controller 550 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and/or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The system controller 550, depending on the processing conditions and/or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and/or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and/or load locks connected to or interfaced with a specific system.

Broadly speaking, the system controller 550 may be defined as electronics having various integrated circuits, logic, memory, and/or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and/or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the system controller 550 in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some embodiments, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and/or dies of a wafer.

The system controller 550, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the system controller 550 may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing steps to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and/or settings, which are then communicated to the system from the remote computer. In some examples, the system controller 550 receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the system controller 550 is configured to interface with or control. Thus as described above, the system controller 550 may be distributed, such as by including one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.

Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and/or manufacturing of semiconductor wafers.

As noted above, depending on the process step or steps to be performed by the tool, the system controller 550 might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and/or load ports in a semiconductor manufacturing factory.

An appropriate apparatus for performing the methods disclosed herein is further discussed and described in U.S. patent application Ser. No. 13/084,399 (now U.S. Pat. No. 8,728,956), filed Apr. 11, 2011, and titled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION”; and Ser. No. 13/084,305, filed Apr. 11, 2011, and titled “SILICON NITRIDE FILMS AND METHODS,” each of which is incorporated herein in its entireties.

The apparatus/process described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels and the like. Typically, though not necessarily, such tools/processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically includes some or all of the following operations, each operation enabled with a number of possible tools: (1) application of photoresist on a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or workpiece by using a dry or plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

EXPERIMENTAL Experiment 1

An experiment was conducted to evaluate the amount of surface contamination from depositing 100 Å of SiN using diiodosilane by ALD on a 12-inch wafer. The metals shown in Table 2 below were evaluated for contamination levels after the film was deposited. Dichlorosilane metals result in surface concentrations greater than 100×10¹⁰ atoms/cm² for aluminum, greater than 5×10¹⁰ atoms/cm² for copper, and greater than 5×10¹⁰ atoms/cm² for iron. As shown in Table 2, metal contamination on the wafer when the silicon nitride film was deposited by diiodosilane was much lower than that of films deposited by dichlorosilane.

TABLE 2 Surface Concentration Method Surface Concentration Detection Limits (×10¹⁰ atoms/cm²) Aluminum (Al) 0.1 <0.1 Calcium (Ca) 0.1 1.9 Chromium (Cr) 0.03 <0.03 Copper (Cu) 0.01 0.083 Iron (Fe) 0.05 0.073 Magnesium (Mg) 0.05 0.45 Nickel (Ni) 0.03 1.8 Potassium (K) 0.1 <0.1 Sodium (Na) 0.1 <0.1 Titanium (Ti) 0.03 0.053 Zinc (Zn) 0.03 0.090

Experiment 2

A Fourier transform infrared spectroscopy (FTIR) spectrum was generated for a silicon nitride material deposited by a diiodosilane and a silicon nitride material deposited by a dichlorosilane. The silicon nitride material deposited by the iodosilane showed only N—H bonding and no generation of unstable Si—H bonds.

Experiment 3

An experiment was conducted for deposition of silicon nitride using tetraiodosilane and deposition of silicon nitride using tetrabromosilane. Deposition of silicon nitride using tetraiodosilane was performed by atomic layer deposition (ALD) using alternating pulses of tetraiodosilane and ammonia at a deposition rate of 0.55 Å/cycle. The resulting film had a step coverage greater than 95%.

Deposition of silicon nitride using tetrabromosilane was performed by ALD using alternating pulses of tetrabromosilane and ammonia at a deposition rate of 0.37 Å/cycle. The resulting film had a step coverage greater than 95%. Note that deposition into a feature having a 14:1 aspect ratio exhibited high conformality and uniformity (see FIG. 6A).

A Fourier transform infrared spectroscopy (FTIR) spectrum was generated for the silicon nitride material deposited by the tetrabromosilane. The FTIR spectra is depicted in FIG. 6B, which identifies peaks and wavelength locations 601, 603, 605, 607, and 609 as follows: 601 represents the Si—N—Si bonds (885 cm⁻¹), 603 represents Si₂N—H bonds (1180 cm⁻¹), 605 represents N—H₂ bonds, 607 represents Si—H bonds, and 609 represents Si₂N—H bonds (3350 cm⁻¹). The silicon nitride material deposited by the tetrabromosilane showed little Si—H bonding and high Si—N—Si bonding.

The density as measured for both films deposited by the tetraiodosilane and the tetrabromosilane were 2.2 g/cc. Both films have high N—H content. Although films exhibited high wet etch rate in 100:1 dilute hydrofluoric acid, these results suggested that bromosilanes is a strong candidate as a silicon precursor for depositing silicon nitride.

Experiment 4

An experiment was conducted involving exposing silicon nitride films deposited by tetrabromosilane to NH₃ plasma. A GST (germanium, antimony, tellurium) substrate without a barrier layer was subject to NH₃ plasma for 60 seconds. The resulting composition of the substrate is depicted in FIG. 7A. The substrate had a Ge:Sb:Te ratio of 1:0.7:1.5.

A barrier layer was deposited on a GST substrate by thermal ALD involving alternating pulses of tetrabromosilane and NH₃. The resulting composition of the substrate is depicted in FIG. 7B. The substrate had a Ge:Sb:Te ratio of 1:0.9:2.0.

A GST substrate including a barrier layer deposited by 107 cycles of thermal ALD involving alternating pulses of tetrabromosilane and NH₃ was exposed to NH₃ plasma for 60 seconds. The resulting composition of the substrate is depicted in FIG. 7C. The substrate had a Ge:Sb:Te ratio of 1:0.9:2.2 As compared to the substrate described above with respect to FIG. 7A, the silicon nitride film deposited using tetrabromosilane prevented the GST substrate from being damaged by the NH₃ plasma.

Experiment 5

An experiment was conducted involving exposing silicon nitride films of different thicknesses deposited by tetrabromosilane to ammonia plasma. Silicon nitride was deposited on a first GST substrate by 60 cycles of thermal ALD involving alternating pulses of tetrabromosilane and NH₃ to form a 22 Å film (thickness calculated using deposition rate of 0.37 Å/cycle). The substrate including the silicon nitride was exposed to 60 seconds of NH₃ plasma. The resulting composition of the substrate is depicted in FIG. 8A. The Ge:Sb:Te ratio was 1:0.9:2.0. Loss of some surface germanium and bulk tellurium was observed.

Silicon nitride was deposited on a second GST substrate by 83 cycles of thermal ALD involving alternating pulses of tetrabromosilane and NH₃ to form a 31 Å film (thickness calculated using deposition rate of 0.37 Å/cycle). The substrate including the silicon nitride was exposed to 60 seconds of NH₃ plasma. The resulting composition of the substrate is depicted in FIG. 8B. The Ge:Sb:Te ratio was 1:0.9:1.9. Loss of some surface germanium and bulk tellurium was observed.

Silicon nitride was deposited on a third GST substrate by 107 cycles of thermal ALD involving alternating pulses of tetrabromosilane and NH₃ to form a 40 Å film (thickness calculated using deposition rate of 0.37 Å/cycle). The substrate including the silicon nitride was exposed to 60 seconds of NH₃ plasma. The resulting composition of the substrate is depicted in FIG. 8C. The Ge:Sb:Te ratio was 1:0.9:2.2. Little to no loss was observed. It can be concluded that a silicon nitride film deposited to a thickness of at least 40 Å using tetrabromosilane as a precursor can sufficiently protect a GST substrate from NH₃ plasma.

CONCLUSION

Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the embodiments are not to be limited to the details given herein. 

1-15. (canceled)
 16. A memory device comprising: a memory stack comprising a chalcogenide material; and a silicon nitride layer deposited over the memory stack and encapsulating the chalcogenide material, the silicon nitride layer deposited to a thickness of at least 40 Å by alternating exposures of a chlorine-free bromine-containing or iodine-containing silicon precursor and a second reactant using atomic layer deposition, the silicon nitride layer having a step coverage of between about 30% and about 90%.
 17. The memory device of claim 16, wherein the iodine-containing silicon precursor is selected from the group consisting of diiodosilane and hexaiodosilane.
 18. The memory device of claim 16, wherein the chlorine-free bromine-containing silicon precursor is selected from the group consisting of compounds having a chemical formula of Si_(x)Br_(y)I_(z), where x=1, y is an integer between and including 1 and 4, and y+z=4; and compounds having a chemical formula of Si_(x)Br_(y)I_(z), where x=2, y is an integer between and including 1 and 6, and y+z=6.
 19. The memory device of claim 16, wherein the chlorine-free bromine-containing silicon precursor is selected from the group consisting of tetrabromosilane (SiBr₄), SiBr₃I, SiBr₂I₂, SiBrI₃, hexabromodisilane (Si₂Br₆), Si₂Br₅I, Si₂Br₄I₂, Si₂Br₃I₃, Si₂Br₂I₄, Si₂BrI₅, and combinations thereof.
 20. The memory device of claim 16, wherein the chalcogenide material is selected from the group consisting of sulfur, selenium, tellurium, and combinations thereof.
 21. The memory device of claim 16, wherein the step coverage of the silicon nitride layer deposited over the memory stack is at least about 95%.
 22. The memory device of claim 16, wherein the silicon nitride layer is greater than about 30 Å thick.
 23. The memory device of claim 16, further comprising a second layer comprising silicon nitride or silicon carbide over the silicon nitride layer and memory stack, wherein the second layer has a step coverage of between about 30% and about 90%.
 24. The memory device of claim 23, wherein the second layer is deposited by remote plasma chemical vapor deposition or plasma enhanced chemical vapor deposition.
 25. The memory device of claim 23, wherein the memory device comprises one or more features, each feature having a top and a bottom and a sidewall, and wherein the second layer is deposited non-conformally and has a thickness on a sidewall of at least one of the one or more features greater at the top of the at least one of the one or more features than a thickness of the second layer on the sidewall of the at least one of the one or more features at the bottom of the at least one of the one or more features.
 26. An apparatus comprising: at least one process chamber comprising a pedestal for holding a substrate; at least one outlet for coupling to a vacuum; one or more process gas inlets coupled to process gas sources; and a controller for controlling operations, comprising machine-readable instructions for: causing introduction of a chlorine-free bromine-containing silicon precursor to the at least one process chamber, the chlorine-free bromine-containing silicon precursor selected from the group consisting of compounds having a chemical formula of Si_(x)Br_(y)I_(z), wherein x=1, y is an integer between and including 1 and 4, and y+z=4; and compounds having a chemical formula of Si_(x)Br_(y)I_(z), wherein x=2, y is an integer between and including 1 and 6, and y+z=6; and causing introduction of a second reactant to the at least one process chamber.
 27. The apparatus of claim 26, further comprising a plasma generator for generating a reactive species, wherein the machine-readable instructions further comprise instructions for causing generation of a plasma when the second reactant is in the at least one process chamber.
 28. The apparatus of claim 27, wherein the plasma generator is a remote plasma generator.
 29. The apparatus of claim 26, wherein the second reactant forms a volatile species when reacted with a material selected from the group consisting of aluminum, iron, copper, antimony, selenium, tellurium, germanium, and arsenic.
 30. The apparatus of claim 26, wherein the pedestal is a heated pedestal and the machine-readable instructions further comprise instructions for causing the heated pedestal to be set at a temperature of less than about 300° C.
 31. An apparatus comprising at least one process chamber comprising a pedestal for holding a substrate; at least one outlet for coupling to a vacuum; one or more process gas inlets coupled to process gas sources; and a controller for controlling operations, comprising machine-readable instructions for: causing introduction of diiodosilane or hexaiodosilane to the at least one process chamber; and causing introduction of a second reactant to the at least one process chamber.
 32. The apparatus of claim 31, further comprising a plasma generator for generating a reactive species, wherein the machine-readable instructions further comprise instructions for causing generation of a plasma when the second reactant is in the at least one process chamber.
 33. The apparatus of claim 32, wherein the plasma generator is a remote plasma generator.
 34. The apparatus of claim 31, wherein the second reactant forms a volatile species when reacted with a material selected from the group consisting of aluminum, iron, copper, antimony, selenium, tellurium, germanium, and arsenic.
 35. The apparatus of claim 31, wherein the pedestal is a heated pedestal and wherein the machine-readable instructions further comprise instructions for causing the heated pedestal to be set at a temperature of less than about 300° C. 